PT100201A - COMPOSITION OF PERSONAL CLEANING BASED ON SOFT LIQUID SOAP - Google Patents

Description

U4.428 Case 4344 R

COMPOSITION OF PERSONAL CLEANING BASED ON LIQUID SOAP

SOFT AND STABLE REFERENCE CROSSED TO A RELATED PATENT APPLICATION This application is a partial continuation of U.S. Patent Application Serial No. 07 / 665,620, filed March 5, 1991.

TECHNICAL FIELD 15

Mod. 71-20,000 ex. The present invention relates to liquid soap products, in particular pumpable facial cleaning compositions and bath / shower compositions which are formulated to exhibit softness, viscosity control and phase stability.

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Liquid personal cleansing compositions are well known. The following U.S. Invention patents disclose these compositions: U.S. Patent 3,697,644, filed by Laiderman and issued October 10, 1972, No. 3,932,610, filed by Rudy et al. and granted January 13, 1976; No. 4,031,306, filed by De-Martino et al. issued June 21, 1977; No. 4,061,602, filed by Oberstar et al. and issued December 6, 1977; No. 4,387,040 filed by Straw and issued June 7, 1983; and No. 4,917,823, filed by Maile, Jr., and issued April 17, 1990; No. 4,338,211, filed by Stiros and issued on July 6, 1982; No. 4,190,549, filed by Imamura et al. and issued February 26, 1980, Number 4,861,507 deposited by Gervasio and issued August 29, 1989; -3- 35 1 5 10

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and British Invention Patent Number 1,235,292, published June 9, 1971, as well as the publication Soap Manu-facturer, Davidson et al., Vol. 1, page 305, 1953. U.S. Patent Number No. 4,673,525, filed by Small et al., Issued June 16, 1987, incorporated herein by reference, discloses personal cleansing systems based on alkyl glyceryl ether sulfonate (AGS) mild surfactants, mainly synthetic bars. Most liquid soaps comprise mostly " unsaturated ", unsaturated " shorter chains, for example lauric / oleic soaps, to achieve phase stability. This, however, compromises the quality of the foam and its soft character. British Patent Specification No. 1,235,292, supra, describes a mixture of K / Na soap; at least 5% of K soap and 0.1 to 5% of alkyl cellulose. Soaps are natural. The natural fatty acids contain a certain degree of unsaturation and therefore have high iodine titres low titers. Liquid soap 292 exemplified contains from about 17% to about 21.5% soap and up to 1% free fatty acid. U.S. Patent No. 4,387,040, mentioned above, discloses a stable liquid K soap containing a viscosity control agent comprised of coconut-DEA and sodium sulfate. Soaps of C12 saturated acids are used. The viscosity of the soap varies from 1 to 1.5 (1000 and 1500 cps) at 25øC, RVT viscometer / rod 3/10 revolutions Some formulations' 040 contain electrolyte and a polymeric thickening agent, but these formulations are said to be unstable It should also be noted that lauric acid soap is a relatively severe soap and when used at higher levels (as used in Ό40) acts against the smoothness of the product

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Newtonian liquids that are too viscous are more difficult to pump than liquids that become thinner by cutting action. The products of " soap " liquid stocks currently on sale on the market are / for the most part, Newtonian and only in very small proportions at moderate proportions are liquids that become more fluid by cutting action. Although it is known that natural potassium (K) soap is used to make liquid cleaning compositions, there are no indications or suggestions for solutions to certain problems encountered with saturated, low-value, super-greasy soaps of high fatty acid (FFA) iodine (IV). Specifically, phase stability, good foam quality, and control of viscosity and stability have not been resolved to date or only partially in the current art. While such liquid soap formulations described above are not subject to or are lesser subject to one or more of the above deficiencies, it is found that improvements in physical stability and stability are desired against variations in rheological properties as a function of time or temperature to increase the shelf life of the product and thereby improve its acceptance by consumers. It is therefore an object of the present invention to provide a bath / shower linseed liquid soap composition which is phase stable, stable in storage, forms good foam and is cosmetically attractive. It is another object of the present invention to provide a liquid soap cleansing composition which is relatively mild. It is yet another object of the present invention

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to provide a viscous, liquid, high shear cleaning composition which is pourable from a container by means of a conventional manual pressure pump. These and other objects of the present invention will become apparent from the detailed description which follows. SUMMARY OF THE INVENTION The present invention relates to a stable, very smooth liquid dispersoid cleaning composition comprising: 55% to 90% water; 5% to 20% of saturated fatty acid potassium soap (small IV 'value) higher (High titre); 2.5% to 18% free fatty acids; said soap and said free fatty acids having a ratio of from 1: 0.3 to 1: 1; and wherein said liquid cleaning composition has a viscosity of from 4 to 100 parts (4,000 to 100,000 cps) at about 25Â ° C; and wherein said liquid cleaning composition is of stable phases. The smooth, stable liquid composition is preferably contained in a vessel having a pressure-actuated pump. The composition is preferably prepared by the steps of: 1. heating and mixing an aqueous mixture of said fatty acid potassium soap and said free fatty acid to give a stable melt; 2. cool the melt to approximately room temperature; and diluting said molten mass cooled with water to obtain said dispersed liquid. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition

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A stable dispersoid liquid soap cleaning composition comprising: 55% to 90%, preferably 60% to 80% water; 5% to 20%, preferably 6% to 14%, of high fatty acid potassium soap, most of which is soluble in-soluble (small IV value), e2.5% to 18%, preferably 3% % to 9%, of free fatty acids. The soap and the free fatty acids have a ratio of from about 1: 0.3 to about 1: 1, preferably from about 1: 0.3 to about 1:: 0.8. The preferred fatty acid material is a mixture of the following saturated fatty acids, based on the total fat content:

Mod. 71 -20,000 ex. - C12 at a level of about 7% + 5%, preferably 7% ± 2%; At a level of about 22% ± 15%, preferably, about 22% ± 5%; - Cig at a level of about 32% ± 10%, preferably 32% ± 5%, more preferably 32% ± 3%; and

30Âμg to a level of about 39% ± 10%, preferably 39% + 5%, most preferably 39% ± 3%. The fatty acid material according to the present invention has an IV of 0 to about 15, preferably less than 10, more preferably less than 3; and a titer of from about 44 to about 70, preferably from about 50 to 68, and more preferably from about 62 to about 65. The liquid soap according to the present invention may be made without a stabilizing ingredient. However, the liquid soap preferably contains from about 0.2% to about 5%, preferably from about 0.3% to about 3%, of a stabilizing ingredient selected from the group consisting of: polymeric thickening agent , 7-35-18

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triol or nonionic compound and mixtures thereof; preferably from 0.1% to 2% thickening agent; 0.1% to 3% of electrolyte? and 0.1% to 2% nonionic compound, and mixtures thereof. One or more of these ingredients improves the stability of liquid soap. The liquid soap has a viscosity of 4-100 parts (4,000-100,000 cps), preferably 10 to 80 parts (10,000 to about 80,000 cps) at about 25Â ° C, determined with a Brookfield viscometer RVTDV / TD rod / 5 revolutions per minute. The preferred composition has a viscosity of from 15 to 70 parts (15,000 to 70,000 cps) and more preferably a viscosity of 30 to 60 parts (30,000 to 60,000 cps). viscosities between about 40 to about 45 parts (about 40,000 to about 45,000 cps) are acceptable. The liquid soap is termed dispersoid because at least some fat at the levels used in its composition is insoluble. The water level in the compositions is typically from about 55% to about 90%, preferably from about 60% to about 80%. The chemical properties of some preferred pure saturated acids having iodine value values equal to 0 are given in the Table of Pure Acids below.

Table of Pure Acids Chain Length Acid value Molecular weight Title ° C Decanoic C-10 326 172 Lauric Cl 2 280 200 44.2 Mystical C-14 246 228 54.4 Pentadecanoic C-15 231 242 Palmitic C-16 219 256 62.9 Margárico C-17 207 270 Stearic C-18 197 280 69.6 -8- 35

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1 Nonadecanoic C-19 188 298 Arachidonic C-20 180 312 Bevénico C-22 165 340 5 The titres of the " natural " are outside the fatty acid material chosen according to the present invention.

Table of Acids of Palm Seed Oil 10 16

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Saturated acid Chain length% by weight Octanoic C-8 3 Decanoic C-10 3 Lauric Cl 2 50 Myristic C-14 18 Palmitic Cl 6 8 Stearic C-18 2 Unsaturated acid Oleic C-18 = 1 14 Linoleic C- 18 = 2 2 iodine content Low 14 High 23 saponification index Low 245 High 255 Title, ° C (fatty acid): Low 20 High 28

Note that the title is low. Table of Acids of Coconut Oil Saturated Acid Chain Length% by Weight Octanoic C-8 7 Decanoic C-10 6 Lauric C-1 2 50 -9- 1 5 10

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M-Ionic content C-18 18 Palmitic Cl 6 8.5 Stearic C-18 3 Unsaturated acid Oleic C-18 = 1 6 Linoleic C-18 = 2 1 Linolenic C-18 = 3 0.5 Iodine content: 5 High 10.5 saponification index: Low 250 High 264 Titre, ° C (fatty acid) Low 20 High 24 The value of the coconut oil acid iodine value is acceptable but its titre is low. Sebum BFT Table Saturated Acid Chain Length% by Weight Miristic C-14 3 Pentadecanoic C-15 0.5 Palmitic C-16 24 Marginate C-17 1.5 Stearic C-18 20 Myristoylic Unsaturated C-14 = 1 1 Palmitoleico C-16 = 1 2.5 Oleic C-18 = 1 43 Linoleic C-18 = 2 4 Linolenic C-18 = 3 0.5 Iodine content: High 45 Low 50 saponification index Low 192-10 - 35 5 10

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Title, ° C (fatty acid) Low High 202 40 45

Another important attribute of the preferred liquid soap according to the present invention is its ability to be pumped, particularly after storage during a temperature cycle. A less preferred liquid product is one in which its initial viscosity is sufficient to be pumped but in which there is an unacceptable increase in its viscosity which renders it non-pumpable upon heating at 45øC for about eight hours and cooling to room temperature. The most preferred liquid soaps according to the present invention may withstand more than one of these cycles. The term " pumpable " as used herein means that the liquid soap may be pumped from a conventional glass or plastic container having a carton type pressure operated manual pump sold by Calmar Co., Cincinnati , Ohio, United States of America, under the registered trade mark of Dispenser SD 200, with a discharge of about 1.7 cubic centimeters of liquid soap. Another standard pump is that sold by Specialty Packaging Products, Bridgeport, Connecticut, United States of America, under the registered trademark of LPD-2 Pump. This pump provides about 1.7 cubic centimeters of lichen. of. &Quot; storage viscosity " or " cyclic viscosity " of a liquid soap product is defined herein as its viscosity after being subjected to one or more temperature cycles. This expression is used to describe the shelf stability or storage of the liquid soaps that are formulated for use in a pump dispenser operated by standard pressure. The preferred product is formulated to provide the stability

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the desired viscosity and foam. It does not become separated or become too viscous after being heated and cooled under ambient conditions. The terms " initial viscosity " and " cyclic viscosity " as used herein are defined according to the processes mentioned herein, unless otherwise noted. Briefly, " cyclic viscosity " is measured after the liquid soap has been subjected to a heating cycle at 49.5 ° C for eight hours and cooling to 25 ° C. The term " viscosity " as used herein means both of these viscosities when measured with a Brookfield RVTDV-II / Haste TD viscometer at 5 revolutions per minute at 25 ° C, unless otherwise specified . The liquid soap product according to the present invention has an initial viscosity of from about 10 to about 70 parts (about 10,000 to about 70,000 cps) and / or a cyclic viscosity of from about 15 to about about 80 p.s. (about 15,000 to about 80,000 cps). The liquid soap product according to the present invention becomes fluid by cutting action. Its viscosity increase factor with the cut-off rate which allows it to be pumped by means of a normal pressure driven manual pump, despite its relatively high viscosity comprised between 10 and 70 parts (10,000 to 70,000 cps ). The preferred liquid soap dispersion has a high flowability per shear action, as defined herein. Its viscosity is reduced by at least a factor of 1.5, preferably at least about 2 and more preferably at least about 3.0% of the fluoride factor. due to shear "is defined as follows: Viscosity under a shear rate equal to 1 second-dl Viscosity at a shear rate equal to 10 seconds -1-12- 35 1 5 10

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The viscosities are measured with a Bohlin VOR rheometer at room temperature (25øC). Note that the following Bohlin viscosities are different from those measured with the Brookfield viscometer. For example, a liquid soap (such as that of Example 1B below) having a Bohlin viscosity of about 38 parts (38,000 cps), at a cut-off rate of about 1 second has a viscosity of Bohlin from about 4 cents (4,000 cps) at a cutoff rate of about 10 seconds. The shear flow factor for this liquid is about 38,000 / 4,000 or about 9,5. Cutting fluency enhancement factors in the case of the present invention range from about 1.5 to about 25, preferably from about 2 to about 20, and most preferably from about 3 to about of 15. Additional viscosity determinations obtained with the Bohlin rheometer demonstrate approximate shear strength factors for some commercially available cleaning fluids and the present invention and are referred to below after the Examples. Preferably, the liquid soap comprises from about 0.2% to a total of about 5%, preferably from about 0.3 to about 3%, of a stabilizing ingredient selected from the group consisting of 0.1% to 2% of a thickening agent; 0.1% to 3% of electrolyte; and 0.1% and 2% nonionic product or mixtures thereof. One or more of these ingredients may improve the stability of liquid soap. The more diluted the liquid, the greater amounts of these stabilizing ingredients can be added.

Thickeners Thickeners according to the present invention are categorized as cano. cationic, nonionic or anionic acids and are selected to provide the

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5 viscosities desired. Suitable thickening agents are listed in the Glossary and in Chapters 3,4, 12 and 13 of the Handbook of Water-Soluble Gums and Reps, Robert L. Davidson, McGraw-Hill Book Co., New York, NY , 1980, which are hereby incorporated by reference.

Liquid personal cleansers may be thickened by means of polymeric additives which hydrate, swell or molecularly associate to provide a body (for example, hydroxypropyl guar gum is used as an auxiliary thickening agent in the shampoo compositions).

Nonionic cellulosic thickening agents include - but are not limited to - the following polymers:

Mod. 71-20,000 εκ. 1. hydroxyethyl cellulose; 2. hydroxymethyl cellulose; 3. hydroxypropylcellulose; and 4. hydroxybutyl-methylcellulose. The anionic cellulosic thickening agent includes carboxymethylcellulose and the like. The preferred thickening agent is xarthan gum, which has a molecular mass of about 2,000,000 ± 500,000. Each molecule has about 2,000 repeating units. Another preferred thickening agent is the acrylate acrylate-20-methyl acrylate copolymer sold as Acrysol ICS-1 by Rohm and Haas Company. The amount of polymeric thickening agent found to be useful in the compositions according to the present invention is from about 0.1% to about 2%, preferably from about 0.2% to about 1%.

Electrolyte 35

An additional requirement is required for

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Preferred compositions according to the present invention are that they contain a low level of electrolyte. The electrolytes include inorganic salts (e.g., potassium chloride or sodium chloride), as well as organic salts (e.g., sodium citrate), potassium acetate). Potassium chloride is preferred. The amount of electrolyte varies with the type of the surfactant system, but should be present in the finished product at a level of from about 0.1% to about 3%, preferably from about 0.25% to about of 2.9%. In addition to the aforementioned chloride and citrate salts, other salts include phosphates, sulfates and other salts of halogenated ions. The counterions of these salts may be sodium or other monovalent cations, as well as bivalent and trivalent cations. It is recognized that these salts may cause instability if they are present at higher levels.

Non-ionic stabilizing agent

Another preferred component of the compositions according to the present invention is a nonionic product. The preferred nonionic product is polyglycerol ester (PGE).

Groups of substances which are particularly suitable for use as nonionic tensioactive agents are fatty alcohols or alkoxylated alkyl phenols, preferably alkoxylated with ethylene oxide or with mixtures of ethylene oxide or propylene oxide; polyglycol fatty acid esters or fatty acid amides; block polymers of ethylene oxide / propylene oxide; glycerol ester and polyglycerol ester; sorbitol esters and sorbitan esters; polyglycol esters of glycerol; ethoxylated lanolin derivatives; and alkanolamides and sucrose esters.

Optional Components

If present, the components

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In general, the individual optional compounds comprise from about 0.001% to about 10% by weight of the composition. The liquid shower bath cleaning compositions may contain a variety of optional non-essential ingredients suitable for making such compositions more desirable. Such conventional optional ingredients are well known to those skilled in the art, for example, preservatives, such as benzyl alcohol, methyl paraben, propyl paraben and imidazolyl urea; other agents: thickeners and viscosity modifiers, such as Câ, â, <â, † alkyl-ethanolamide (e.g., coconut-eta-nolamide alkyl) and polyvinyl alcohol; pear humectants, such as glycerin; pH adjusting agents such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, etc .; suspending agents, such as magnesium silicate / aluminum silicate; Perfumes; dyes; sequestering agents, such as disodium ethylenediamine tetraacetate.

Tensioactive agent An important property of the personal liquid soap cleansers preferred according to the present invention is their rich and creamy foam. The preferred composition also contains from about 1% to about 10%, preferably from about 2% to about 6%, of high foaming synthetic surfactant. An important optional component of the present compositions is a surfactant which enhances foaming. The tensioactive agent, which may be selected from any of a wide variety of anionic (other than soap), amphoteric, hydrophilic, nonionic and, in certain cases, tensioactive agents cationic surfactants is present at a level of from about 1% to about 10%, preferably from about 2% to about 6% by weight of the liquid product. 35

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Mod. 71-20,000 ex. - 90/08 20 The patent literature on cleaning products is full of indications of synthetic surfactants. Some preferred surfactants as well as other ingredients of the cleaning products are referred to in the following references:

Pat. No. Date of granting Inventors 4,061,602 12/1977 Oberstar et al. 4,234,464 11/1980 Morshauser 4,472,297 9/1984 Bolich et al. 4,981,539 1/1985 Hoskins et al. 4,540,507 9/1985 Grollier 4,565,647 1/1986 Filling 4,673,525 6/1987 Small et al. 4,704,224 11/1987 Saud 4,788,006 11/1988 Bolich, Jr., et 4,812,253 3/1989 Small et al. 4,820,447 4/1989 Medcalf et al. 4,906,459 3/1990 Cobb et al. 4,923,635 5/1990 Simion et al. 4,954,282 9/1990 Rys et al. J 25

All of the patents mentioned are hereby incorporated by reference. A preferred synthetic surfactant is cited in the Examples herein. Preferred synthetic surfactant systems are selectively designed by their appearance, stability, foaming, cleaning properties and softness. 30

It should be noted that the mildness of the surfactant can be measured by means of a skin barrier destruction test which is used to assess the irritation potential of the surfactants. In this test, the smoother the surfactant, the less the skin barrier is destroyed. The destruction of the skin barrier is measured by the relative amount of radioactively labeled water (H-1 → O) passing from the test solution through the epidermis

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/ t / from the skin to the physiological buffer contained in the chamber with the diffused liquid. This assay is described by T.J.Franz in J.L. Invest. Dermatol., 1975, 64, pages 190-195 and in U.S. Patent No. 4,673,525, filed by Small et al. and issued June 16, 1987 incorporated herein by reference and which relates to a mild alkyl-glyceryl ether sulphonate (AGS) surfactant based on a synthetic bar comprising a mixture of ether sulfonate alkyl glycerol "standard. &quot; The barrier destruction assay is used to choose the mild surfactants. Some preferred mild surfactants are described in the aforementioned patents of Small et al. and Rys et al. Some examples of good mild suds-enhancing detergent detergent agents are, for example, sodium or potassium lauryl sarcosinate, alkyl-glyceryl ether sulfonate, sulfonated fatty esters and goi acids of the sulfonates. Numerous examples of other tensioactive agents are mentioned in the patents incorporated herein by reference. They include other alkyl sulphates, anion acyl sarcosine cations, methyl acyl taurates, N-acyl glutamates, acyl isethionates, alkyl sulfo succinates, alkyl phosphate esters, ethoxylated alkyl phosphate esters , tri-deceth sulfates, protein condensates, mixtures of ethoxylated alkyl sulfates and alkylamine oxides, betaines, sultaines and mixtures thereof. The alkyl ether sulfates having one to twelve ethoxy groups, especially sodium and ammonium lauryl ether sulphate, are included in the tensioactive agents. The alkyl chains for these thiosioactive agents are Î ± -CHâ,, - alkyl chains, and the methyl esters are preferred soft nonionic agents which may be mixed with other mild anionic or amphoteric surfactants in the compositions. 35

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Mod. 7] -20,000 ex. In accordance with the present invention, Alkyl polyglycoside detergents are useful urethane foam reinforcing agents. The alkyl group may range from about eight to about twenty-two and the glycoside units per molecule may range from about 1.1 to about 5 to provide the appropriate balance between the hydrophilic and hydrophobic moieties of the molecule , preferred C 12 -C 16, C 12 -C 16 alkyl combinations of polyglycosides having average degrees of glycosidation of from about 1.1 to about 2.7, preferably about 1.2 to about about 2.5. Anionic surfactants other than soap may be exemplified by the alkali metal salts of organic products resulting from the reaction of sulfuric acid which have in their molecular structure an alkyl radical containing from eight to twenty-two carbon atoms and a sulfonic acid ester or sulfuric acid radical (the term &quot; alkyl &quot; includes the alkyl moiety of the higher acyl radicals). Preferred are sodium, ammonium, potassium or triethylammonium alkyl sulphates, especially those obtained by sulphating the higher alcohols (C--C g g carbon atoms) / monoglycerides sulphates and sulphonates of coconut oil fatty acids and of sodium? sodium or potassium salts of sulfuric acid esters of the reaction products of 1 mole of a higher fatty alcohol (for example, tallow or coconut oil alcohols) and 1 to 12 moles of ethylene oxide; sodium or potassium salts of alkyl phenol-ethyl ether oxide sulphate with one to ten ethylene oxide units per molecule in which the alkyl radicals contain from eight to twelve carbon atoms, alkyl glyceryl ether- sodium sulfonate; the fatty acid reaction products having from ten to twenty-two carbon atoms esterified with i -hexanoic acid and neutralized with sodium hydroxide; water soluble salts of condensation products of fatty acids with sarcosine; and others known in the art. 35 1

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Hybrid surfactants may be exemplified by those which are broadly described as derivatives of aliphatic phosphonium quaternary ammonium and sulfonium compounds, wherein the aliphatic radicals may be straight chain or branched chain and wherein one of the substituents aliphatic radicals contains from about eight to eighteen carbon atoms and one contains a water-soluble anionic group, for example carboxy, sulfonate, sulfate, phosphate or phosphonate. A general formula for these compounds is as follows

(R3) X

R 2 - Y (+) - CH 2 - R 4 - Z 15

Mod. 71-20,000 ex. - 90/08 20 &gt; In which R 2 contains an alkyl, alkenyl or hydroxyalkyl radical of from about eight to about eighteen carbon atoms, from zero to about ten ethylene oxide groups and from zero to a glyceryl group; Y is selected from the group consisting of nitrogen, phosphorus and sulfur atoms; R3 is an alkyl or monohydroxy alkyl group containing one to about three carbon atoms; X is 1, when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom; R4 is an alkylene or hydroxyalkylene of one to about four carbon atoms; and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate and phosphate groups. Examples include 4- [N, N-di (2-hydroxyethyl) -N-octadecylammonium] -butane-1-carboxylate; 5- [S-3-hydroxypropy1-hexadecylsulfonium] -3-hydroxypentane-1-sulfate; 3- [p, p-diethyl-β-3,6,9-trioxa-tetradeoxy-phosphonium] -2-hydroxy-propane-1-phosphate; 3- [N, N-dipropyl-N-3-dodecyloxy-2-hydroxy-propylammonium] -propane-1-phosphonate; 3- (N, N-dimethyl-N-hexadecylammonio) propane-1-sulfonate; 3- (N, N-dimethyl-N-hexadecyl) -20-35

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mononium) -2-hydroxypropane-1-sulfonate; 4- [N, N-di- (2-hydroxy-ethyl) -N- (2-hydroxydodecyl) -ammonio] -butane-1-carboxylate; 3- [S-ethyl-S- (3-dodecyloxy-2-hydroxypropyl) sulfonium] -propane-1-phosphate; 3- (p, p-dimethyl-β-dodecylphosphonium) -propane-1-phosphonate; and 5- [N, N-di- (3-hydroxypropyl) -N-hexadecylammonio] -2-hydroxypentane-1-sulfate. examples of amphoteric surfactants which may be used in the compositions according to the present invention are those which may be broadly described as derivatives of secondary and tertiary aliphatic amines, wherein the aliphatic radical may be straight or branched chain and wherein one of the aliphatic substituents contains from about eight to about eighteen carbon atoms and one contains an anionic solubilizing group in water, for example carboxy, sulfonate, sulfate, phosphate or phosphonate. examples of compounds which fall within this definition are sodium 3-dodecylamino-propionate, sodium 3-dodecylaminopropane sulfonate, N-alkyl taurines, such as the preparation by reacting dodecylamine with sodium isethionate according to the disclosures of U.S. Patent No. 2,658,072, N-higher alkyl aspartic acids, such as those produced according to the teachings of U.S. Patent No. 2,438,091 and the products sold under the designation commercial &quot; Miranol &quot; and described in U.S. Patent No. 2,528,378. Other amphoterics, such as betaines, are also useful in the compositions according to the present invention. Examples of betaines useful in accordance with the present invention include the higher alkyl betaines, such as coconut dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha carboxyethyl betaine, dimethyl carboxymethyl betaine, lauryl bis (2-hydroxyethyl) carboxymethyl betaine, stearyl bis (2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma carboxyethyl betaine 1 5

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laureth-bis- (2-hydroxypropyl) -alpha-carboxyethyl betaine, etc. The sulfobetaines may be represented by coco-dimethyl-1-sulfopropyl betaine, stearyl dimethylsulfopropyl betaine, lauryl bis- (2-hydroxyethyl) -sulfopropyl betaine, amidobetaines, starch sulfo betaines and the like. Many cationic surfactants are known in the art. By way of example, the following may be mentioned: stearyl dimethyl benzyl ammonium chloride; dodecyl-trimethylammonium chloride; nonyl-benzyl-ethyl-dimethylammonium nitrate; tetradecyl-pyridinium bromide; lauryl-pyridinium chloride; cetyl-pyridinium chloride; lauryl pyridinium chloride; lauryl-isoquinolium bromide; tallow (hydrogenated) -dimethylammonium dialkyl chloride; dilauryl dimethylammonium chloride; and stearalkonium bromide. Many additional different deminerating agents are described in McCutcheon's Detergents and Emulsifiers, 1979 Annual, published by Allured Publis-hing Corporation, which is hereby incorporated by reference. The above-mentioned surfactants can be used in liquid bath / shower cleaning compositions according to the present invention. Anionic surfactants, particularly the alkyl sulfates, the ethoxylated alkyl sulfates and mixtures thereof are preferred. More preferred are the anionic C 12 -C 14 alkylene-surfactants selected from the group consisting of sodium alkyl glycerol ether sulfonate, sodium lauryl sarcosinate, sodium alkyl sulfate, ethoxy (3) - sodium sulphate and mixtures thereof. Nonionic surfactants may be broadly defined as compounds produced by the condensation of (hydrophilic) alkylene oxide groups with a hydrophobic organic compound which may be aliphatic or alkyl aromatic in nature. Examples of preferred classes of nonionic surfactants are those which are preferred,

64,428 Case 4344 And following: 1. the condensed polyethylene oxide products of alkyl phenols / for example the condensation products of alkyl phenols having an alkyl group containing from about six to twelve carbon atoms with with either straight chain or branched chain configuration with ethylene oxide, said ethylene oxide being present in amounts ranging from 10 to 60 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent of these compounds may be derived from polymerized propylene, diisobutylene, octane or nonane, for example. 2. 15

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The condensation derivatives of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine products, which may vary in position depending on the balance between the hydrophobic and the hydrophilic elements desired. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a base hydrophobic composition comprising the reaction products of ethylene diamine and excess of propylene oxide, said base having a molecular weight in the range of 2,500 to 3,000. The product of the condensation of aliphatic alcohols having from eight to eighteen carbon atoms, with a straight or branched chain configuration, with ethylene oxide, for example, a condensation of coconut alcohol with ethylene oxide having ten to thirty moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol moiety having from ten to fourteen carbon atoms. Other products of ethylene oxide condensation are ethoxylated fatty acid esters of

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64,428 Case 4344 R / o polyhydric esters (for example / Tween 20, polyoxyethylene (20) sorbitan monolaurate). 4. Long-chain tertiary amine oxides corresponding to the following general formula wherein R 1 contains an alkyl, alkenyl or monohydroxyalkyl radical having from about eight to about eighteen atoms of carbon, from zero to about ten ethylene oxide groups and from zero to a glyceryl group; and R 2 and R 3 contain from one to about three carbon atoms and from zero to about one hydroxy group, for example methyl, ethyl, propyl, hydroxyethyl or hydroxypropyl radicals. The arrow in the formula is the conventional representation of a semi-polar link. Examples of amine oxides suitable for use in the present invention include dimethyl dodecylamine oxide, oleyl di- (2-hydroxyethyl) amine oxide, dimethyl octylamine oxide, dimethyl-decylamine oxide, di- methyl-tetradecylamine oxide, 3,6,9-trioxaheptadecyldiethylamine oxide, di- (2-hydroxyethyl) -tetradecylamine oxide, 2-dodecyloxyethylmethylamine oxide, 3-dodecyloxy-2- hydroxypropyl-di- (3-hydroxypropyl) -amine, dimethylhexadecylamine oxide. oxides of long chain tertiary phosphines corresponding to the following general formula RR 'R &quot; In which R contains an alkyl, alkenyl or monohydroxyalkyl radical containing from eight to eighteen carbon atoms in the chain length, from zero to about ten ethylene oxide groups and from zero to one glyceryl grouping; 35 1 35

15

Mod. 71-20,000 ex. - 90/08 20

30

64.428 Case 4344 R

Jít. i &gt;

7 and R 'and R &quot; are each alkyl or monohydroxyalkyl groups containing from one to three carbon atoms. The arrow in the formula is the conventional representation of a semi-polar link. Examples of suitable phosphine oxides are: dodecyl dimethyl phosphine oxide, tetradecyl methyl ethyl phosphine oxide, 3,6,9-trioxa-octadecyl dimethyl phosphine oxide, cetyl dimethyl phosphine oxide, phosphine, 3-dodecyloxy-2-hydroxypropyl-di- (2-hydroxyethyl) phosphine oxide, stearyl dimethyl phosphine oxide, cetyl ethyl propyl phosphine oxide, oleyl diethyl phosphine oxide, dodecyl diethyl phosphine oxide, tetradecyl di-ethyl phosphine oxide, dodecyl dipropyl phosphine oxide, dodecyl di- (hydroxymethyl) phosphine oxide, dodecyl di- (2-hydroxyethyl) -phosphine oxide, tetradecylmethyl-2-hydroxypropyl phosphine oxide, oleyl dimethyl phosphine oxide, 2-hydroxydodecyldimethylphosphine oxide. 6. Long chain dialkyl sulfoxides containing a lower alkyl or hydroxyalkyl radical having one to about three carbon atoms (generally methyl) and a long hydrophobic chain containing alkyl, alkenyl, hydroxyalkyl or heteroaryl radicals and having between about eight to about twenty carbon atoms, from zero to about ten ethylene oxide groupings and from zero to a glyceryl grouping. Examples include octadecyl methyl sulfoxide, 2-keto-tridecyl methyl sulfoxide, 3,6,9-trioxa-octadecyl-2-hydroxyethyl sulfoxide, dodecylmethyl sulfoxide, oleyl-3-sulfoxide hydroxypropyl methyl sulfoxide, 3-methoxy tridecyl methyl sulfoxide, 3-hydroxy tridecyl methyl sulfoxide, 3-hydroxy-4-dodecyloxy-butyllithium sulfoxide. The pH of the liquid cleaning compositions is

1 64,428 Case 4344 R

bath / shower according to the present invention is generally from 8 to about 9.5 / preferably from about 8.5 to about 9, as measured in a 10% aqueous solution at 25 ° C. Manufacturing process

10J 16

Mod. 71-20,000 ex. - 90/08 20 J 25 30

The liquid soap cleansing compositions according to the present invention may be prepared using the techniques described in the Examples. The preferred process for the manufacture of the stable liquid compositions comprises: 1) an aqueous (35 to 60% water) soap mixture: FFA is heated to give a melt of stable phases (liquid crystals); 2) the melt is cooled to room temperature to give a cream with stable phases; and 3) diluting the cream in water to provide a stable dispersion of liquid soap. These operations are preferably carried out under vacuum but the use of vacuum is not essential. The vacuum can be replaced by other deaeration methods, for example, centrifugation. The dilution water preferably contains 0.5% PGE, 0.5 electrolyte and 0.2% polymeric thickening agent to improve storage stability. Preferred liquid soap has a stable storage viscosity of from about 10 to about 80 parts (about 10,000 to about 80,000 cps) (RVTDV-II, Rod TD, 5 revolutions per minute). A viscosity of 45 parts (± 15 pairs) (45,000 cps (± 15,000 cps)) is ideal to distribute this liquid (with high shear rate factor) by means of a normal piston actuated displacement pump the personal cleaning. The preferred liquid soap may be formulated so as to be very mild using a small concentration of soap and selected higher saturated soap fatty acid chains. When a foam-enhancing surfactant, for example, sodium or potassium lauroyl sarcosyate (2.5%) is added, the liquid soap pre-

64,428 Case 4344 R -ΜΠ992 wound has very good foam characteristics. Liquid soap cleansing compositions are useful as cleansing aids for the entire body. The basic invention may also be applicable to other liquid-type products, such as hand-washing liquid soaps. The following methods are used to evaluate liquid soap compositions.

15

Mod. 71-20,000 e *. - 90/08 20 Method I Initial viscosity (product at 100%) Apparatus: Brookfield RVTDV-II Viscometer, Helipath, Rod TD, 115 grams (4 ounce) sampling cylinder. Conditions: Sample temperature equilibrated at room temperature (23 ° C / 72 - 77 ° F) / Brookfield viscometer at 5 revolutions per minute. Method:

25 30

Approximately 120 mL of product is transferred to the 115 gram sample (4 oz) beaker, being careful not to let air enter. Allow to equilibrate at room temperature for at least four hours. Calibrate and adjust the viscometer to zero according to the Brookfield manual. With the TD rod installed, the viscometer rotating at 5 revolutions per minute and the helipath control connected to the chain (downward direction), lower the viscometer until the rod almost touches the surface of the product. It is observed when the helipath assembly moves the rod through the surface of the product and, as soon as the rod is dipped, the time is counted. After thirty seconds the following five viscosity readings are recorded. These readings are averaged and recorded. If the viscosity of the liquid soap is between about 10 - 27 - 35

64,428 Case 4344 R 5

15

Mod. Η - 20,000 ex. - 90 ° C to about 100 parts (about 10,000 to about 100,000 cps), then the soap passes this test Method IIA - Viscosity Cycle (product at 100 °) Apparatus - Brookfield RVTDV-II Viscometer , Helipath, Haste TD, sample beaker of 115 grams (4 oz) / ambient temperature or constant water bath at about 49 ° C (120 ° F) .Conditions: The sample on heating cycles from room temperature (RT ) to 49.5 ° C and return to room temperature The residence time of the sample at 49.5 ° C shall be at least 8 hours and when it cools the residence time at RT shall be at least equal to 8 hours before the viscosity is measured The viscometer rotates at approximately 5 revolutions per minute Method:

30

Approximately 120 mL of the product is transferred to the 115-gram (4-ounce) sample beaker being careful not to let air enter. The sample is placed at constant room temperature of 49.5 ° C in an oven or water bath. Store the product at this temperature for at least eight hours. The product is transferred to room temperature and allowed to equilibrate for at least eight hours. Calibrate and adjust the viscometer to zero according to the Brookfield manual. With the TD rod installed, the viscometer at 5 revolutions per minute and with the helipath control in operation (downshift), lower the viscometer until the rod almost touches the surface of the product. It is observed when the assembly 28-35 1

64.428 Case 4344 R

5 helipath moves the rod through the surface of the product and, as soon as the rod is submerged, the time of thirty seconds is counted, and then the following five viscosity readings are recorded. These readings are averaged and recorded. If the viscosity of the liquid soap is comprised between 10 and 100 parts (10,000 and 100,000 cps), then it passes this test and is considered the most preferred liquid. 10

Method IIB It is the same as Method IIA, but T = 37.8 ° C. Method III - Accelerated Stability

Device:

Centrifuge with temperature control capability or constant room temperature, glass jar of 25 - 30 ml.

Conditions :

Centrifugal samples with approximately 350 grams and temperature of 49.5 ° C (120 ° F). Method: 25 30

Approximately 25 ml of product is transferred to the glass vial taking care not to enter air. The sample is placed in an atmosphere at 49.5 ° C for at least two hours to equilibrate. The vial is placed in the centrifuge with a controlled atmosphere of 49.5 ° C. Centrifuge at about 350 g (350 X force of gravity) at 1200 rotations per minute for four hours. Remove from the centrifuge and observe, note the separation of the product, if any, and record the result. If the liquid soap passes in this case, it is greatly preferred.

EXAMPLES -29- 35 1 £ 19½ 5 10 15

Mod. 71-20,000 ex. - 90/08 20

30

64,428 Case 4344 R /

The following Examples describe and demonstrate preferred embodiments within the scope of the present invention. The Examples are described for the purpose of illustration only and are not intended to serve as a limitation of the present invention since many variations are possible without departing from its spirit and scope. Unless otherwise noted, all percentages and proportions referred to herein are approximations and by weight. The following Example 1B refers to a preferred dispersed liquid soap according to the present invention. The Brookfield viscosity of Example 1B is about 30 Pa.s (30,000 cps). The iodine value of the fatty acids of Example 1 is about 0 and its titer is about 59 ° C. Example 1B has totals of about 10.2% soap, 6.85% free fatty acid and 2.4% sarcosinate. The ratio of soap to free fatty acid (FFA) is about 1: 0.67. TABLE 1 EXAMPLE 1 Formula 1A 1 B Ingredients% by weight% by weight Stearic Acid 7.55 4.53 Palm + Ionic acid 6.23 3 74 Myristic Acid 8.72 5.23 Acidic Acid 3.52 2.11 Trichlosan 0 , 30 0.18 KOH (87%) 3.86 2.32 Glycerin 15.00 9.00 * Mayoquest (45%) 0.44 0.26 Lauroyl Sodium Sarcosinate 13.33 8.00 -30 35

"64,428 Case 4344 R

JR-400 0.50 0.30 Aloe Vera Powder 0.01 iH o Perfume 0.30 0.18 Toral Water (approx.) 70.00 Mayoquest is a blend in the ratio of 50/50 of

HEDP / DPTA

15

A liquid soap (Example 18) is prepared by first mixing the ingredients of &quot; IA &quot; as follows: 1. All fatty acids are mixed and melted with Triclosan in a jacketed vessel and heated to 80 ° C. 2.

Mod. 71-20,000 ex. - 90/08 20 3. 4.

25 30 5.

KOH tablets are dissolved with water in order to prepare a 38 wt% solution. Sodium or potassium glycerol / lauryl sarcosinate, JR-400, Mayoquest and water are mixed in a separate jacketed vessel and heated to 80 ° C. The molten fatty acid mixture of Step 1 is transferred to a vacuum vessel containing an internal homogenizer, wall scrapers and blade mixers; for example, a Mizuho series automated vacuum type emulsifier, model APVQ-3DP sold by Mizuho Industrial Co., Ltd. or a T.K. AGI model 2M-2, manufactured by Tokushu Kika Kogyo Co., Ltd. Although the vacuum is not essential, it is very preferred so that the intermediate has a specific gravity of about 1 + 0.05. The KOH solution is slowly added under vacuum of about 400 mm Hg, while mixing and homogenizing during saponification. While mixing, the temperature is maintained at 80 ± 5 ° C. After the saponification is complete, the water mixture from Step 3 is added under vacuum, at -31-35 ° C.

Mod. 71-20,000 ex. - 90/08

64,428 Case 4344 R DUKMQ '1 while continuing to mix and homogenize. The temperature is maintained at 80 ± 5 ° C while mixing to obtain a stable melt phase. 7. Immediately begin to cool from 80øC to 50øC at the rate of 3øC per minute. The mixture is maintained and the vacuum is maintained during the cooling operation but the homogenization is stopped. 8. 10 15 20 &gt; 25 30 9. 10

The true alloying powder is dissolved in water and added at 50 ° C. Cool from 50 ° C to 35 ° C at the cooling rate of 0.5 ° C per minute, under vacuum, while mixing. At 35 ° C, the vacuum is quenched and the perfume is added. Continue to cool while mixing until the final blend reaches about 30 ° C. At about 30 ° C, cooling is stopped, and the vessel mixture is discharged. 11. The cooled melt from Operation 10 (IA) is diluted with distilled water at about room temperature. First the water and the cooled melt are gently mixed to give a uniform suspension and then transferred to the vessel under vacuum from Step 4 and homogenised for about ten minutes under about 600 mm Hg to give an aqueous liquid soap dispersion (70% water) (Example 1B). Liquid soaps can be manufactured by varying this process, but the simple mixing of the ingredients of Example 1B does not result in obtaining a stable liquid dispersoid. EXAMPLES 2-6 -32-35

64.428 Case 4344 R

Examples 2 to 6 relate to liquids manufactured using the procedure of Example 1, except that the following stabilizing ingredients (percentage relative to the finished liquid soap) were added to the dilution water of Example 11: KCl / 5% PGE 0/5%

Xanthan 0.2%

Examples 2 to 5 and Comparative Example 6 15 20

Ingredients 2; 3: 4 5 6 wt% wt% wt% wt% wt% Soap 10.2 5.0 5.0 20.0 20.0 FFA 6.8 5.0 2.5 10.0 20 , Water 81.8 88.8 91.3 68.8 58.8 Total 100.0 100.0 100.0 100.0 100.0 Soap: FFA 1: 0.66 1: 1 1: 0.5 1: 0.5 1: 1 Briefly, Examples 2 to 6 are prepared by proceeding as follows: 1. An aqueous (about 50% water) mixture of the soap is heated: FFA to give a stable casting (Operation 6 above). 2. The melt is cooled to approximately room temperature; and 3. the cooled melt is diluted with water to provide a liquid soap. The dilution water used in Run 3 contains KCl, PGE and xanthan gum. The liquid soap of Example 2 has a viscosity, measured with Brookfield field viscometer, equal to 28 parts (28,000 cps). The mixture of Example 2 has a high melt flow increasing value by the action of color

10J 16

Mod. 71 -20,000 ex.-90 (08 20 J 25

64,428 Case 4344 R e is ideal for dispensing by means of a standard piston driven pump for personal cleaning. The Exeir pio 2 blend is relatively mild due to its low soap concentration and the longer chain saturated soap content. The IV value is less than 1 and the titer is about 59.5 for the fat used in Examples 2-6. The fat of the liquid soaps used in Examples 2-6 is C. 2 to 13% ± 2%; 35% ± 5% C14; C15 to 24% ± 3%; and Cjg at 29% ± 3%, relative to the total fat base. The compositions of Examples 2 = 5 are stable liquid dispersions under standard conditions. The mixtures of Examples 4 and 5 separate under voltage conditions defined below as the Accelerated Stability Method III. However, the samples of Examples 4 and 5 may be rendered more stable by raising the levels of the stabilizing ingredients and / or increasing the titre to a value greater than 60. The blend of Example. Experimental Comparative 6 gels. The soaps of Examples 2 and 3 are stable and stable in storage stages. The mixture of Example 2 is preferred to the mixture of Example 3 because it has a better foam. The preferred liquid soap, for example that of Example 2, has a very rich creamy foam. However, in some of the following Examples, a foam-enhancing surfactant, sodium lauryl sarcosinate or potassium lauryl sarcosinate (2.4%) is added to strengthen the rich, creamy foam. In the following Examples 7-24, the ingredients referred to by the respective trade names are as follows:

Mayoquest is a blend in the 50/50 ratio of HEDP / DPTA. Triclosan is an antimicrobial agent. JR-400 is polyquaternium 10. Capmul 8210 is a mixture of caprylic / capric acid monoglycerides / diglycerides (molecular mass 250). Caprol ET is a mixture of C12-C18 polyglycerol esters (2300 molecular mass). 30

64.428 Case 4344 R

Caprol 10G-4-0 is decaglycerol tetraoleate (molecular mass 1800).

Acrysol ICS is a polymeric thickening agent as defined above. TABLE 3 EXAMPLES 7-9 8 10% by weight% by weight 15

Mod. 71-20,000 ex. - 90/08 20 25 30 35

Ingredients% by weight Stearic Acid 4.53 4.53 5.13 Palmitic Acid 3.74 3.74 4.18 Myristic Acid 5.23 5.23 2.87 Lauric Acid 2.11 2.11 0.87 Triclosan 0 , 18 • 0.18 0.18 KOH (87%) 2.32 2.32 2.32 Glycerin 9.00 9.00 9.00 Mayoquest (45%) 0.26 0.26 0.26 Lauroyl Sarcosinate de Sodium (30%) 8.00 8.00 Lauroyl Potassium Sarcosinate (30%) - - 8.00 JR-400 0.30 or 0.30 Aloe Vera Powder 0.01 0.01 IH o Perfume 0 , 18 CO-IO 0.18 KCl 0.50 - 1.35 K-Acetate (55%) - 1.20 - Caprol ET 0.50 0.50 0.50 Xanthan molecular mass - 64,428

Case 4344 R

1 5

(2,000,000) 0.20 Water D.I. 62.94 Accelerated Stability Passes Viscoside Initial (Pa.s) 22 Cyclic Viscosity at 120 ° F (49 ° C) 49 0.20 0.20 62.24 64.65 Pass Pass 16 14,400 50 10 u 15

Mod. 71-20,000 ex. · 90/08 20 or 25 30

Cyclic Viscosity and 38øC (100øF) (Pa.s) 163-20 Examples 7 and 8 relate to two completely liquid dispersed soap compositions with different electrolytes. The mixture of Example 7 contains 0.5% KCl and 2.4% of the high foaming synthetic surfactant. The mixture of Example 8 contains 1.20 X 0.55 or 0.66% of an active base of acetate K. Both have acceptable viscosities. The mixture of Example 7 is highly preferred. The total soap content is equal to 10.2% and total FFA is equal to 6.84%. The soap / FFA ratio is equal to 1: 0.67. The mixture of Example 7 is mild as the most important mild liquid surfactants. The mixture of Example 9 is more preferred because its viscosity, after treatment of a temperature cycle at 38 ° C (100 ° F), is equal to 20 Pa.s (20,000 cps) compared to 163 pa.s ( 163.Λ300 cps) from Example 7. The total soap content in the case of Example 9 is equal to 10.2% and the total FFA content is 4.2% and the foam-enhancing surfactant is lauroyl potassium arcosinate. The title equals 62 and the soap / FFA ratio is equal to 1: 0.41. The soap from Example 9 is also mild soap as personal cleansers based on mild synthetic surfactants. The levels of electrolyte, acetate K, in Ex.

64.428 Case 4344 R

are set up to have a molar concentration equal to the level of KCl used in Example 7. A &quot; Accelerated Stability &quot; (Method III) is to keep the liquid soaps at 120 ° F (49.5 ° C) for four hours under a centrifuge (1200 rotations per minute).

10 J

&Quot; Viscosities &quot; are measured at about 25øC (RT) using a Brookfield RVTDV-II viscometer with a Helipath drive assembly and a TD / Rod at 5 revolutions per minute, unless other different conditions are specified.

Mod. 71-20,000 ex. - 90/08 15 20 &gt; TABLE 4 EXAMPLES 10-12 12 11 12 Invenuents% by weight% by weight% by P 'Stearic Acid 4.53 4.53 4.53 Palmitic Acid 3.74 3.74 3.74 Myrtic Acid 5.23 5 , 23 5.23 Lauric Acid 2.11 2.11 2.11 Triclosan 0.18 0.18 0.18 KOH (87%) 2/32 2.32 2.32 Glycerin 9.00 9.00 9.00 Mayoquest 0.26 0.26 0.26 Lauroyl Sodium Sarcosinate (30%) 8.00 8.00 8.00 JR-400 0.30 0.30 0.30 Aloe Vera Powder 0.01 0.01 0 , 01 Perfume 0.18 0.18 0.18 KCl 0.50 - - Capmul 8210 0.50 - - -37 35

"64,428 Case 4344 R

Acrysol ICS '- 0-, 80 - Hydroxyethylcellulose - - 0.80 (Molecular weight (350 000-400 000) - - Xanthan (molecular mass 2 000 000) 0.20 - - Water DI 62.94 63.34 63.34 Stability Accelerated Passage Small Small Initial Viscosity (Pa.s) 30 58 48 Cyclic Viscosity (Pa.s) 160 140 200 20 25 The soap from Example 10 contains 0.5% KCl, 0.50% Capmul 8210 and 0.20 % of xanthan The soaps of Examples 11 and 12 do not contain KCl and contain 0.80% of Acrysol ICS and 0.80% of HEC respectively The water levels in these Examples are slightly higher due to the lower amount of the ingredients The soaps of Examples 11 and 12 fail in the accelerated stability test but are stable dissooside liquid soaps under conditions which are stable, The soaps of Examples 11 and 12 were they stop only slightly under accelerated stability test conditions. 30

Compared Example 10 to Example 16 below are identical, except for the lack of the low molecular weight non-ionic Capmul 8210 (250) from Example 10, which appears to have a negative effect on the stability of the cyclic viscosity. Example 13 (hereinafter) has an identical formulation. The nonionic compound thereof is Caprol ET,

64,428 Case 4344 R having a molecular mass (2300) greater than Capmul 8210. The higher molecular mass of Caprol ET appears to have a positive effect on the viscosities after multiple cycles. EXAMPLES 13-16

Mod. 71-20,000 ex. - 90/08 10 16 20

J 25 30 13 14 15 16 Ingredients% by weight% by weight% by weight% by weight Stearic Acid 4.53 4.53 4.53 4.53 Palmitic Acid 3.74 3.74 3.74 3.74 Myristic 5.23 5.23 5.23 5.23 Lauric Acid 2.11 2.11 2.11 2.11 Triclosan 0.18 0.18 0.18 0.18 KOH (87%) 2.32 2, 32 2.32 2.32 Glirecine 9.00 9.00 9.00 9.00 Mayoquest 0.26 0.26 0.26 0.26 Lauroyl Sarcosinate Sodium (30%) 8.00 8.00 8.00 8.00 JR-400 0.30 0.30 0.30 0.30 Aloe Vera powder 0.01 0.01 0.01 0.01 Perfume 0.18 0.18 0.18 0.18 KCl, 50 - 0.50 0.50 Caprol ET 0.50 0.50 0.50 - Xanthane 0.20 0.20 - 0.20 Water DI 62.94 63.44 63.14 63.44 Accelerated Stability Pass Pass Pass Pass Initial Viscosity 35 -39- 64,428

Case 4344 R

(Pa.s) 22 Cyclic Viscosity (Pa.s) 49 42 46 24 185 37 40 10 15

Mod. 71-20,000 ex. - 90/08 20

The soaps of Examples 13, 15 and 16, highly preferred, all have initial and cyclic viscosities acceptable to be pumpable and pass the accelerated stability test. The liquid soaps of Examples 13, 15 and 16 have acceptable cyclic viscosities and contain 0.5% KCl. Note that the soap of Example 14 does not contain electrolyte as a cyclic viscosity stabilizer and has an unacceptably high cyclic viscosity (185 parts-185,000 cps). The soap from Example 15 does not contain xanthan but has an acceptable cyclic viscosity. Caprol ET is a non-ionic product of higher molecular weight (2,300) and does not destroy cyclic viscosity, in contrast to the lower molecular weight nonionic product that is used in Example 10. EXAMPLES 17-19 or 25 30 35 17 18 19 Ingredients% by weight% by weight% by weight Stearic Acid 4.53 4.53 4.53 Palmitic Acid 3.74 3.74 3.74 Myristic Acid 5.23 5.23 5.23 Lauric Acid 2.11 2.11 2.11 Triclosan 0.18 0.18 0.18 KOH (87%) 2.32 2.32 2.32 Glycerin 9.00 9.00 9.00 Mayoquest 0.26 0.26 0.26 Lauroyl Sarcosinate -40

64,428 Case 4344 E

/

Mod. 71-20,000 e *. 20) 25 30 Sodium (30%) 8.00 8.00 8.00 JR-400 0.30 0.30 0.30 Powder of Aloe Vera 0.01 0.01 0.01 Perfume 0.18, 18 0.18 KCl 0.50 - - Caprol ET - - 0.50 Xanthan - 0.20 - DI Water 63.64 63.94 63.64 Accelerated Stability Pass Failure Failure Initial Viscosity (Pa.s) 37 11 24 Cyclic Viscosity (Pa.s) 35 222 180

The soaps of Examples 17 to 19 all have acceptable initial viscosities. The soap from Example 17 has pr. acceptable properties. As in Example 14 the soaps of Examples 18 and 19 do not contain electrolyte. The soap of Example 17 contains 0.50% KCl and those of Examples 18 and 19 have no viscosity stabilizing electrolyte. The soaps of Examples 18 and 19 also failed the accelerated stability test, but at room temperature they are liquid soaps of stable phases. TABLE 7 EXAMPLES 20 22 20 21 22

Ingredients Stearic Acid Palmitic Acid% by weight 4.53 3.74% by weight 4.53 3.74% by weight 4.53 3.74 -41 35

Mod. 71-20,000 ex. - 90/08

J 64,428 Case 4344 R 'Ak $ 1 Myristic Acid 5.23 5.23 5.23 Lauric Acid 2.11 2.11 2.11 Trichlosan 0.18 0.18 0.18 5 KOH (87%) 2.32 2.32 2.32 Glycerin 9.00 9.00 9.00 Mayoquest 0.26 0.26 0.26 Lauroyl Sarcosinate 10 Sodium (30%) 8.00 8.00 8.00 JR-400 0.30 0.30 0.30 Powder of Alloys Vera 0.01 0.01 0.01 Perfume 0.18 0.18 0.18 15 KC1 0.50 - 0.50 K-Acetate (55%) - 1.20 - Caprol ET 0.50 0.50 0.50 20 Xanthan 0.20 0.20 - Water DI 62.94 62.24 63.14 The soaps of Examples 20 to 22 were tested for viscosity stability after multiple cycles. Their initial viscosities and after multiple cores are given in the following Table in Pa s 20 21 22 Initial 24 16 46 Cycle 1 44 50 37 30 Cycle 2 38 80-rl00 35-75 Cycle 3 26 60 28-45 Cycle 4 38 65 30-45 Cycle 5 35-60, -42-35 64,428

Case 4344 R

1 10 15

Mod. 71-20,000 ex. - 90/08 20

TABLE 8 EXAMPLES 23-25 Inerts 23% by weight 24% by weight 25% by weight Stearic Acid 4.53 4.53 4.53 Palmitic Acid 3.74 3.74 3.74 Myristic Acid 5.23 5.23 5.23 Lauric Acid 2.11 2.11 2.11 Triclosan 0.18 0.18 0.18 KOH (87%) 2.32 2.32 2.32 Glycerin 9.00 9.00 9.00 Mayoquest 0 , 26 0.26 0.26 Lauroyl Sodium Sarcosinate (30%) 8.00 8.00 8.00 JR-400 0.30 0.30 0.30 POWE of Aloe Vera 0.01 0.01 0.01 Perfume 0.18 0.18 0.18 KCl 0.50 0.50 0.50 Caprol 10G-4-0 - - 0.50 Xanthan 0.20 - 0.20 Water DI 63.44 63.64 62.94

The viscosities after multiple cycles (Pa.s) of the soaps of Examples 22 to 24 are set forth below:

23 24 25 Initial 24 6 N / A Cycle 1 40 43 N / A Cycle 2 60-70 25-50 N / A -43- 30 1 5 10 16

Mod. 71-20,000 ex. - 90/08 20

64.428 Case 4344 R

Cycle 3 60 45-75 N / A Cycle 4 115 120-180 N / A Cycle 5 - 75-130 N / AN / A = not available The liquid cleaning composition preferably has an initial viscosity of about 15 to about 70 (about 15,000 to about 70,000 cps) and a cyclic viscosity of about 15 to about 80 parts (about 15,000 to about 80,000 cps); the cyclic viscosities of about 20 to about 25 parts (about 20,000 to about 25,000 cps) are very good. A series of Examples was prepared to study the stability phase of the dispersed liquids. The levels of soap / fatty acid concentration are variable, see Table 9. TABLE 9 EXAMPLES 26-29 Soap Concentration Series (without stabilizing ingredients)

Ingredients 26 27 28 29% by weight &amp; wt% Wt% Soap 9.35 10.2 11.05 11.9% FFA 6.27 6.84 7.41 7.98 Sahb / FFA ratio 1: 0.67 1: 0.67 1: 0.67 1: 0.67 Stability Accelerated Failure Failure Failure Failure Viscosity 44-64.428

Case 4344 R

Initial 23 Cyclic Viscosity 110 38 50 55 145 155 155 10 15

Mod. 71 -20,000 ex. - 90/08 20

Soap blends of Examples 26 to 29 without stabilizer at ambient temperature are all formed by stable liquid dispersoidal phases, with initial acceptable viscosities; but all fail in the accelerated stability test, which is performed under the above test conditions. See Method III above for details. TABLE 10 EXAMPLES 30-32

Effect of the Distribution of the Acid Chain Length

Fatty% Soap = 10.2% FFA = 6.84

These formulations also contained the stabilizing ingredients (0.2% xanthan, 0.5% KCT, 0.5% PGE) Ingredients% wt% C12 of the total FA mixture 13, 5% C14 of the total AF mixture 33.5% C15 of the total AF mismatch 24% of total FA 29 31 32 wt% 100 wt%

64,428 Case 4344 R 10 15

Mod. 71-20,000 ex. - 90/08 20 25 30

Accelerated Stability Passes Viscosity Initial (Pa.s) 28 Cyclic viscosity (Pa.s) 79,200 Foam in the hands Good Titre point ° C 59,5

Pass 15,200 740 Sufficient 44.2

Pass 17,200 Very weak 69.6

The mixtures of Examples 30 to 32 are formulated in the same manner as in Example 2, but with the difference of their fatty acid chains. In Example 30, a preferred blend of the soap chain is used. They all pass the accelerated stability test. With respect to cyclic stability, a mixture containing some higher fatty acid chains and titre of about 59.5 ° C is preferred. Note that the blends of Examples 30 and 27 are the same but which, in the case of Example 30, have stabilizers, which provide stability for their cyclic viscosity and accelerated stability. TABLE 11 EXAMPLES 33-35 Effects of Distribution of Fatty Chain Acids% Soap = 10.2% FFA = 6.84 These formulations also contained stabilization ingredients (0.2% Xanthan, 0.5 % KCl, 0.5% PGE) -46-35

64.428 Case 4344 R

Mod. 71-20,000 ex. Ingredient% by weight% by weight% by weight 5% by weight of the mixture of total FA 50 62.5 12.5% of C14 of the total FA mixture - 12.5 12.5% of the blend 10 FA total - 12.5 12.5 Cjg of the total FA mixture 50 12.5 62.5 15 Accelerated Stability Passes Initial Viscosity (Pa.s) 3,200 Pass 13 Pass 4,400 Cyclic Viscosity (Pa.s) 336 210 66.800 Foam in the hands Sufficient Moderate Low 20 Titre Point ° C 56.9 50.9 The mixtures of Examples 33 to 35 63.7 are the same as in Example 2 except for the soap chains. All of them pass the accelerated stability test. Blends having longer chains and having titers of about 59/5 ° C or greater are preferred because of the cyclic stability.

The initial viscosities of the mixtures of E-examples 33 and 35 may be increased with the use of more thickening agent and salt in the formulation. 30

Referring to Table 12 below, three additional liquid soaps are prepared using the same formula but with IV values equal to 11.8 and 5 and with titers equal to 54.8, 55.9 and 57.4, respectively; all of them pass the accelerated stability test and have initial and cyclic viscosities respectively equal to 24 and 53 Pa.s -47 35 10

64,428 Case 4344 R 15

Mod. 71-20,000 ex. - 90/08 20 25

tlUX-5. (24,000 and 53,000 cps); 5.2 and 60.8 Pa.s (5,200 and 60,800 cps) and 3.2 and 36 Pa.s (3,200 and 36,000 cps). TABLE 12 EXAMPLES 36-39 The Effect of Saturation% Sabao = 10.2% FFA = 6.84

The soaps of Examples 36 to 39 also contain: 0.50% PGE, 0.5% KCl and 0.2% Xanthan 36 Ingredients% by weight iodine value 1.0 Accelerated Stability Passes Initial Viscosity (Pa.s ) 28 Cyclic viscosity (Pa.s) 79 Foam in the hands Good 37 38 39% by weight% by weight% by weight 14 20 30 Pass Pass Pass 29,800 57,600 13 175 105 26 Very weak Very weak Weak 30

The most preferred iodine value values are less than 1 for stability and foaming reasons. A further benefit of the low iodine value values is the absence of rancidity odors due to the oxidation of the unsaturated double bond. TABLE 13 EXAMPLES 40-42 The Effect of Thickening Agents -48-35

64,428 Case 4344 R one% Sabao = 10.2% FFA = 6.84

Sage / FFA ratio = 1: 0.67 40 41 42

Ingredients 10 15% by weight% by weight% by weight

Type of Thickening Agent Acrisol Hydroxy ethyl Xanthan

Cellulose Level in the finished product 0,80% 0,80% 0,20% Accelerated Stability Very small Very small Fault Viscosity Initial (Pa.s) 58 48 30 Cyclical Cisco (Pa.s) 140 200 160

Mod. 71 -20,000 ex. Table 13 shows that: 1) the thickening agents improve the stability of the blending formula; 2) Thickening agents by themselves (without electrolyte) do not seem to help the stability of the cyclic viscosity. TABLE 14 EXAMPLES 43-45 The Effect of Non-Tonic Products (Polyglycerol Esters)% Soap = 10.2% FFA = 6.84

Soap / FFA ratio = 1: 0.67

Formulas also contain: 0.50% KCl and 0.2% Xanthan -49-35 64,428

Case 4344 R 43 44 45 Inerventives% by weight% by weight% by weight Non-ionic product Caprol ET Caprol 10G-4-0 Capmul 821C Finished product level 0.50 0.50 0.50 Accelerated stability Pass Pass Pass Initial viscosity ( Pa (s) 22 26 22 Cyclic viscosity (Pa.s) 49 31 260 Caprol ET - mixed polyglycerol esters (HLB = 2.5 chain lengths in c12 'c14 / c16' c18 '6-10 units of glycerol ; molecular mass = 2300)

Caprol 10G-4-0-decaglycerol tetraoleate (HLB = 6.2, molecular mass = 1800).

Capmul 8210-mono / diglycerides of caprylic / capric acids (HLB = 5.5-6.0, molecular mass = 250) Table 14 shows that: 1) nonionic compounds having the highest molecular weight (greater than about 1,000) improve the cyclic viscosity in the presence of electrolyte.

Increased Fluidity Factors Due to Cutting Action

Example Viscosity at Viscosity at 1 sec.-1 (Pa.s) 10 sec.-1 (Pa.s) increase in flowability 1B 38.036 4.003 9.5 A 12.800 2.495 5 B 7.450 5.522 1.35 C 4,220 4,734 0.89 D 2,680 3,533 0.76 -50- 1 1 5 10 15

Mod. 71-20,000 ex. - 90/08

64.428 Case 4344 R

Examples A, B, C and D pertain to commercially available liquid personal cleansing compositions, all packed in pressure-actuated pump containers. &quot; A &quot; is D0Ve (r) Beauty Wash, which is indicated to be a &quot; different soap product &quot;. &quot; B &quot; is LIQUID IV0RY soap which is a soap-based product of K. &quot; C &quot; is the Jer-gens liquid soap and is a synthetic surfactant based product. &quot; D &quot; is Liquid Dial. The soap of Example 1B has a very high viscosity at a cut-off rate of 1 second. but its higher shear flow factor (9.5) makes it possible to easily pump it out by means of a pressure-actuated pump. The liquid forms of Examples B, C and D have small shear flow factors and therefore their viscosities are small to ensure the possibility of being pumped. The soap of Example 1B according to the present invention is three times more viscous than D0Ve (R) Beauty Wash and has an increase in flowability due to cutting about 2 times that of D0VE Beauty Wash. A viscous product with a high shear factor is very desirable both in terms of the possibility of being pumped and the properties of use.

MSCQ MARQUES Ltm Ag? The invention relates to a method for the preparation of a compound of the formula: ## STR1 ## in which R 1 is as defined in formula (I). LMNK -51-35

Claims (1)

64.428 Case 4344 R = CLAIMS = wool. A very soft, dispersed, liquid soap-based personal cleansing composition which is preferably contained in a container having a pressure-actuated pump, characterized in that it comprises (A) from about 5% to about 20% by weight of potassium fatty acid soap; (B) from about 2.5 to about 18% by weight of free fatty acid in C6 -C22 '' and (C) from about 55% to about 90% of water; and wherein said fatty acid of constituents (A) and (B) has an iodine value of from about C to about 15; and a title (° C) of from about 44 to about 70; wherein said soap and said free fatty acid have a weight ratio of from about 1: 0.3 to about 1: 1; and wherein said product has a viscosity of from about 4 Pa.s (4000 cps) to about 100 Pa.s (100 cps) at 25 ° C. 2â. The liquid cleaning composition according to claim 1, wherein said iodine value value is less than 5 and said title is from about 50 to about 70. A liquid cleaning composition according to claim 1, characterized in that said iodine value value is less than 3 and said titer is from about 62 to about 70. A liquid cleaning composition according to claims 1, 2 or 3, characterized in that it comprises from about 6% to about 14% by weight of said potassium soap and from about 3% to about 9% by weight of said free fatty acid and from about 1% to about 10% by weight of a synthetic surfactant which gives rise to a large amount of foam. -52- 1 5 10 15 Mod. 71-20.0 0 0 ex. - 90/08 20 25 5â. A liquid cleaning composition according to claim 1, characterized in that the ratio of potassium soap to the free fatty acid is from about 1: 0.3 to about 1: 0.8; and said fatty acid being predominantly saturated and having an iodine value of from zero to about 10; and said fatty acid is composed of alkyl groups having the chain lengths between Cg and C22 &gt; and said fatty acid has a titer of from about 62 to about 70; and said composition contains from about 2% to about 6% of a synthetic surfactant which gives rise to a large amount of foam; and said product having a viscosity of from about 10 Pa.s to about 70 Pa.s (about 10,000 cps to about 70,000 cps); and preferably said fatty acid has an iodine value value of zero to 3 and said synthetic surfactant is lauroyl sarcosacinate of cations selected from the group consisting of sodium or potassium and mixtures thereof; and said composition having a shear strength increased by shearing stress comprised between at least 1.5 and about 25, preferably between about 2 and about 20, and most preferably between about 3 and about 15.6. The liquid cleaning composition according to claim 1, wherein said fatty acid has chain lengths from C20 to C187. A liquid cleaning composition according to claims 1, 2, 3, 4, 5 or 6, characterized in that it contains from about 60% to about 80% water; from about 6% to about 14% of said fatty acid potassium soap; from about 3% to about 9% of said free fatty acid; and said fatty acid has an iodine value of from about zero to about 3 and said viscosity is from about 10% to about 60% . 908-20 and about 70 Pa.s (about 10,000 to about 70,000 cps). 8ã. Dispersed liquid soap cleaning compositions according to claims 1, 2, 3, 4, 5, 6 or 7, characterized in that it is prepared by the following operations: 1. heating and mixing an aqueous mixture quenching the fatty acid potassium soap and quot; free fatty acidquot; to give a stable melt; Cooling the melt to approximately room temperature; and (3) diluting said molten mass cooled with water to obtain said dispersed liquid. 9a. The liquid dispersion-based cleaning composition according to claim 8, characterized in that said cooled melt of step 2 is stable; and preferably said soap and said free fatty acid of step 1 are heated to a temperature in the range of about 75 ° C to about 90 ° C; and preferably includes the deaeration operation of said liquid said cooling being effected at a rate of about 0.5 ° C per minute or less. JLft 1992 ¥ ÀSCO MARQUES Iffff Age · <Ο | ι | *.?,. · - Industrial Gift-Arc® ao Conceição, 3,! -1 / 96 UMMI -54-35